Oxime ethers, compositions containing them and the use thereof

ABSTRACT

The oxime ethers of the formula I below are able to act as antidotes or safeners to protect cultivated plants from the phytotoxic effects of herbicides. Such cultivated plants are preferably sorghum, cereals, maize and rice, and herbicides are principally chloroacetanilides and thiocarbamates. The oxime ethers have the formula I ##STR1## wherein n is 1 or 2, each of R 1  and R 2  is hydrogen or C 1  -C 4  alkyl each of R 3  and R 4  is hydrogen, halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, C 1  -C 4  alkylthio, C 1  -C 4  haloalkylthio, C 1  -C 4  alkylsulfinyl, C 1  -C 4  alkylsulfonyl, C 1  -C 4  haloalkylsulfinyl, C 1  -C 4  haloalkylsulfonyl or nitro; each of R 5  and R 6  independently of the other is C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 2  -C 8  alkoxyalkyl, C 3  -C 4  alkenyl, C 3  -C 4  alkynyl, or together form a 2- to 6-membered alkylene or alkenylene bridge which may be substituted by 1 to 4 C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 2  -C 4  alkenyloxy, C 2  -C 8  alkoxyalkyl or C 3  -C 8  alkenyloxyalkyl groups; each of A and B independently of the other is oxygen or sulfur, or one of A and b is the methine group, X is a fluorinated C 1  -C 3  alkyl radical which may also additionally contain chlorine, and Y is hydrogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy or phenyl.

This is a divisional of application Ser. No. 473,905 filed on Mar. 10,1983, now U.S. Pat. No. 4,530,716.

The present invention relates to novel oxime ethers, to the preparationthereof, to compositions for protecting cultivated plants from thephytotoxic effects of herbicides, which compositions contain the noveloxime ethers as active component, and to the use thereof.

It is known that herbicides belonging to a very wide range of compoundclasses such as triazines, urea derivatives, carbamates, thiocarbamates,haloacetanilides, halophenoxyacetic acids etc., when employed in aneffective concentration, often also damage cultivated plants to acertain extent in addition to the weeds which it is desired to control.To counteract this problem, different compounds have already beenproposed which are able specifically to antagonise the harmful action ofthe herbicide on the cultivated plant, i.e. to protect the cultivatedplant without noticeably influencing the herbicidal action on the weedsto be controlled. However, it has been found that the proposed antidotesvery often have a species-specific activity both with respect to thecultivated plants and to the herbicide and also, in some cases,contingent on the mode of application, i.e. a specific antidote is oftensuitable only for a specific cultivated plant and a few classes ofherbicides.

For example, British patent specification No. 1 277 577 describes theprotective treatment of seeds or seedlings of wheat and sorghum withcertain oxamic acid esters and amides against attack by ALACHLOR(N-methoxymethyl-N-chloroacetyl-2,6-diethylaniline). Antidotes fortreating cereals, maize and rice seeds against the harmful effects ofherbicidal thiocarbamates are proposed in German Offenlegungsschriftspecification Nos. 1 952 910 and 2 245 471 and in French patentspecification No. 2 021 611. German patent specification No. 1 576 676and U.S. Pat. No. 3,131,509 disclose the use of hydroxyaminoacetanilidesand hydantoins for protecting cereal seeds against the effects ofcarbamates.

The direct pre- or postemergence treatment of certain useful plants withantidotes as antagonists of specific classes of herbicides in a croparea is disclosed in German Offenlegungsschrift specification Nos. 2 141586 and 2 218 097 and in U.S. Pat. No. 3,867,444.

Further, German Offenlegungsschrift No. 2 402 983 discloses that maizeplants can be effectively protected against damage by chloroacetanilidesby adding an N-disubstituted dichloroacetamide as antidote to the soil.

According to European patent application No. 11.047,alkoximinobenzylcyanides, in which the alkoxy group is substituted,inter alia, by an acetalised carbonyl group, can also be used asantidotes for protecting cultivated plants from the harmful effects ofherbicides belonging to different classes of compounds.

The present invention relates to novel oxime ethers of the formula I##STR2## wherein n is 1 or 2, each of R₁ and R₂ is hydrogen or C₁ -C₄alkyl each of R₃ and R₄ is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄haloalkylthio, C₁ -C₄ alkylsulfinyl, C₁ -C₄ alkylsulfonyl, C₁ -C₄haloalkylsulfinyl, C₁ -C₄ haloalkylsulfonyl or nitro; each of R₅ and R₆independently of the other is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₂ -C₈alkoxyalkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, or together form a 2- to6-membered alkylene or alkenylene bridge which may be substituted by 1to 4 C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkenyloxy,C₂ -C₈ alkoxyalkyl or C₃ - C₈ alkenyloxyalkyl groups; each of A and Bindependently of the other is oxygen or sulfur, or one of A and B is themethine group, X is a fluorinated C₁ -C₃ alkyl radical which may alsoadditionally contain chlorine, and Y is hydrogen, C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy or phenyl.

The C₁ -C₄ alkyl groups represented by or contained in the radicals R₁to R₆ may be straight chain or branched and are individually methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.Among these alkyl groups, C₁ -C₂ alkyl groups are preferred and R₁ asalkyl is preferably methyl.

Halogen denotes fluorine, chlorine, bromine and iodine, with fluorineand chlorine being preferred.

The fluorinated alkyl radical X may be e.g. difluoromethyl,trifluoromethyl, chlorodifluoromethyl, tetrafluoroethyl,pentafluoroethyl, difluorochlorofluoroethyl and heptafluoropropyl. Amongthese radicals X, perfluorinated alkyl radicals are preferred in whichone fluorine atom may be replaced by a chlorine atom. Particularlypreferred radicals X are trifluoromethyl, chlorodifluoromethyl andpentafluoroethyl.

Depending on the significance of A, B and Y, different ether orthioether derivatives are obtained. Where each of A and B is oxygen, Yis hydrogen and each of R₅ and R₆ is alkyl, alkenyl or substitutedalkyl, acetals are obtained. Where R₅ and R₆ together form an alkyleneor alkenylene bridge, cyclic acetals are obtained, e.g. 1,3-dioxolanes,1,3-dioxane, 1,3-dioxepane or 1,3-dioxep-5-one derivatives as well ashigher dioxo ring systems.

Where each of A and B is sulfur, Y is hydrogen and each of R₅ and R₆ isa hydrocarbon radical, thioacetals are obtained. Where R₅ and R₆together form a hydrocarbon bridge, dithiolones and dithianes areobtained.

Where each of A and B is oxygen and Y is alkyl or phenyl, ketals areobtained. Thioketals are obtained if A and B are sulfur.

Orthoesters are obtained where each of A and B is oxygen, Y is alkoxyand each of R₅ and R₆ is a hydrocarbon radical. Cyclic orthoesters areobtained where R₅ and R₆ together form a hydrocarbon bridge.

A may also be oxygen, B methylene and Y hydrogen, and R₅ and R₆ togetherform a hydrocarbon bridge, to give furane, dihydrofurane,tetrahydrofurane, pyrane, di- or tetrahydropyrane derivatives andsimilar oxygen ring derivatives.

Different preparatory methods are often employed for these types ofcompounds.

The following variants of compounds of the formula I are possible:##STR3##

The oxime ethers of the formula I accordingly take the form of thefollowing subgroups, for example as

(a) acetal derivatives of the formula II ##STR4## wherein n, R₁, R₂, R₃,R₄ and X are as defined for formula I and each of R₅ and R₆independently of the other is C₁ -C₄ haloalkyl, C₂ -C₈ alkoxyalkyl, C₃-C₄ alkenyl or C₃ -C₄ alkynyl, i.e. they may be the same or differentand are e.g. methyl, ethyl, propyl, isopropyl, butyl, chloroethyl,bromoethyl, methoxyethyl, allyl or propargyl;

(b) ortho-esters of the formula III ##STR5## wherein n, R₁, R₂, R₃, R₄and X are as defined for formula I, each of R₅ and R₆ independently ofthe other is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₂ -C₈ alkoxyalkyl, C₃ -C₄alkenyl or C₃ -C₄ alkynyl and Y is C₁ -C₄ alkoxy;

(c) ring derivatives, e.g. the 1,3-dioxane, 4,7-dihydro, 1,3-dioxepinecompounds of the formulae IV and IVa ##STR6## wherein n, R₁, R₂, R₃, R₄,A, B and X are as defined for formula I, each of m and p is 0 or 1, 2 or3, R₇ is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₂ -C₈ alkoxyalkyl oralkenyloxyalkyl, preferably methyl. Those ring derivatives are preferredin which A and B are oxygen and have the formula V ##STR7## wherein n,R₁, R₂, R₃, R₄ and X are as defined for formula I and R₅ and R₆ togetherform a 2- to 6-membered alkylene or alkenylene bridge which may besubstituted by 1 to 3 C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₂ -C₈ alkoxyalkylor alkenyloxyalkyl groups.

Among these compounds, the following are in turn preferred:

(d) compounds in which n is 1, each of R₁, R₂, R₄ and Y is hydrogen, R₃is in the 4-position and is hydrogen, halogen, methyl, difluoromethyl,trifluoromethyl, chlorodifluoromethyl, methoxy, difluoromethoxy,trifluoromethoxy, chlorodifluoromethoxy, tetrafluoroethyl,tetrafluoroethoxy or trifluoromethylsulfonyl, each of A and B is oxygen,X is trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl, and R₅and R₆ are as defined for formula I;

(e) compounds in which n is 1, each of R₁, R₂, R₄ and Y is hydrogen, R₃is in the 4-position and is hydrogen, fluorine, chlorine, methyl,difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy,difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy,tetrafluoroethyl, tetrafluoroethoxy or trifluoromethylsulfonyl, each ofA and B is oxygen, X is trifluoromethyl, chlorodifluoromethyl orpentafluoroethyl, and R₅ and R₆ together are a 1,2-ethylene or1,3-propylene group which is unsubstituted or substituted by 1 to 4methyl, chloromethyl, C₁ -C₄ alkoxy or C₂ -C₄ alkenyloxy groups;

(f) compounds in which n is 1, R₁, R₂ and R₄ are hydrogen, R₃ is in the4-position and is hydrogen, fluorine, chlorine, methyl, trifluoromethylor trifluoromethoxy, each of A and B is oxygen, X is trifluoromethyl,chlorodifluoromethyl or pentafluoroethyl, and R₅ and R₆ together are a1,2-ethylene group which is unsubstituted or substituted by 1 to 4methyl groups:

(g) compounds in which n is 1 each of R₁, R₂, R₄ and Y is hydrogen, R₃is in the 2-position and is fluorine or chlorine, each of A and B isoxygen and R₅ and R₆ together are a 1,2-ethylene or 1,3-propylene groupwhich is unsubstituted or substituted by 1 to 4 methyl groups; and

(h) compounds in which n is 1, each of R₁, R₂, R₄ and Y is hydrogen, R₃is in the 3-position and is trifluoromethyl or nitro, each of A and B isoxygen, X is trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl,and R₅ and R₆ together are a 1,2-ethylene or 1,3-propylene group whichis unsubstituted or substituted by 1 to 4 methyl groups.

Preferred individual compounds are:

1-phenyl-B 1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane,

1-(4-chlorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane,

1-(4-chlorophenyl)-1-(2,2-diethoxyethoximino)-2,2,2-trifluoroethane,

1-(4-chlorophenyl)-1-(2,2-dimethoxyethoximino)-2,2,2-trifluoroethane,

1-(4-fluorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane,

1-(3,4-dimethylphenyl-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane,

1-(4-fluorophenyl)-1-(1,3-dioxolan-4-methyl-2-ylmethoximino)-2,2,2-trifluoroethane,

1-phenyl-1-(1,3-dioxan-2-ylmethoximino)-2,2,2-trifluoroethane,

1-(3-trifluoromethylnaphthyl)-1-(1,3-dioxan-2-ylmethoximino)-2,2,2-trifluoroethane,

1-phenyl-1-(1,3-dioxolan-2-ylmethoximino)-2,2,3,3,3-pentafluoropropane,

1-(4-chlorophenyl)-1-(1,3-dioxolan-2-ylethoximino)-2,2,2-trifluoroethane,

1-(4-fluorophenyl)-1-(1,3-dioxan-2-ylmethoximino)-2,2,2-trifluoroethane,

1-(4-fluorophenyl)-1-(1,3-dioxolan-2-ylethoximino)-2,2,2-trifluoroethane,

1-(4-chlorophenyl)-1-(1,3-dioxolan-4,5-dimethyl-2-ylmethoximino)-2,2,2-trifluoroethane,

1-(3-trifluoromethylphenyl)-1-(1,3-dioxolan-4-ethyl-2-ylmethoxyimino)-2,2,2-trifluoroethane.

The novel oxime ethers of the formula I are prepared by reacting a saltof an oxime of the formula VI ##STR8## in which M is an alkali metalcation or an alkaline earth metal cation and R₂, R₃, R₄ and X have theabove meanings, with a haloalkyl ether of the formula VII ##STR9## inwhich Hal is a halogen atom, preferably a chlorine atom or a bromineatom, and A, B, n, R₁, R₅ and Y are as defined above. Suitable salts ofan oxime of the formula VI are in particular the sodium and potassiumsalts. The reaction of the oxime of formula VI with the haloalkyl etherof formula VII is conveniently carried out in an inert organic solvent.Particularly suitable solvents are polar solvents such as acetonitrile,dimethylformamide and dimethylsulfoxide.

The reactants are normally employed in equimolar amount. However, anexcess of one or other reactant may also be employed to bring thereaction to completion. The reaction is conveniently carried out atelevated temperature, preferably in the range from 60° to 70° C.

The oximes of formula VI may be prepared in known manner by reacting thecorresponding ketones with hydroxylamine. The ketones required for thereaction can in turn be obtained by reacting a Grignard compound of theformula VIII ##STR10## wherein Y is chlorine, bromine or iodine, and R₂,R₃ and R₄ are as defined above, with a carboxylic acid X--COOH, an acidchloride X--COCl or a nitrile X--CN, each derived from the radical X asdefined above (cf. U.S. Pat. No. 3,748,361). Further, it is alsopossible to obtain ketones suitable for preparing the oximes of formulaVI by reacting a benzene of the formula IX ##STR11## in which R₂, R₃ andR₄ are as defined above, with a carboxylic acid chloride X--COCl derivedfrom the radical X as defined above, in the presence of aluminiumchloride.

Examples of oximes of the formula VI which are suitable for obtainingthe novel oxime ethers of the formula I are:

1-phenyl-1-hydroxyimino-2,2,2-trifluoroethane

1-(4-methylphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-chlorophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-fluorophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-trifluoromethylphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3-trifluoromethylphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-methoxyphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-trifluoromethoxyphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3-nitrophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3,4-dimethylphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3,4-dichlorophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-chlorophenyl)-1-hydroximino-2,2-difluoroethane

1-(4-chlorophenyl)-1-hydroximino-2-chloro-2,2-difluoroethane

1-(4-methoxyphenyl)-1-hydroximino-2-chloro-2,2-difluoroethane

1-(4-trifluoromethoxyphenyl)-1-hydroximino-2-chloro-2,2-difluoroethane

1-(3-nitrophenyl)-1-hydroximino-2-chloro-2,2-difluoroethane

1-phenyl-1-hydroximino-2,2,3,3,3-pentafluoropropane

1-(4-methylphenyl)-1-hydroximino-2,2,3,3,3-pentafluoropropane

1-(4-chlorophenyl)-1-hydroximino-2,2,3,3,3-pentafluoropropane

1-(3-nitrophenyl)-1-hydroximino-2,2,3,3,3-pentafluoropropane

1-phenyl-1-hydroximino-2,2,3,3,4,4,4-heptafluorobutane

1-(4-chlorophenyl)-1-hydroximino-2,2,3,3,4,4,4-heptafluorobutane

1-(2-chlorophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(2-fluorophenyl)-1-hydroximino-2,2,2-trifluoroethane.

The haloalkyl ethers of formula VII can be prepared by reacting ahalogenated alkanol of the formula VIIa ##STR12## wherein n, Hal and R₁are as defined above, in known manner, with a C₁ -C₄ alkanol ormercaptan, or with a corresponding 1,2-, 1,3-, 1,4- or 1,5-alkanediol, a1,4-alkenyldiol or with a corresponding dimercaptan.

Examples of suitable haloacetals of the formula III are:

1,1-dimethoxy-2-bromoethane

1,1-dimethoxy-2-bromopropane

1,1-diethoxy-2-bromoethane

1,1-dimethoxy-3-bromopropane

1,1-diethoxy-3-bromobutane

1,3-dioxolan-2-ylmethyl bromide

1-(1,3-dioxolan-2-yl)-1-bromoethane

1-(1,3-dioxolan-2-yl)-2-bromoethane

1-(1,3-dioxolan-2-yl)-2-bromopropane

4,5-dimethyl-1,3-dioxolan-2-ylmethyl bromide

4,4,5,5-tetramethyl-1,3-dioxolan-2-ylmethyl bromide

4,4-dimethyl-1,3-dioxolan-2-ylmethyl bromide

1-(4,5-dimethyl-1,3-dioxolan-2-yl)-1-bromoethane

1-(4,5-dimethyl-1,3-dioxolan-2-yl)-2-bromoethane

1-(4,5-dimethyl-1,3-dioxolan-2-yl)-2-bromopropane

1,3-dioxan-2-ylmethyl bromide

1-(1,3-dioxan-2-yl)-1-bromoethane

1-(1,3-dioxan-2-yl)-2-bromoethane

1-(1,3-dioxan-2-yl)-2-bromopropane

5,5-dimethyl-1,3-dioxan-2-ylmethyl bromide

4,4-dimethyl-1,3-dioxan-2-ylmethyl bromide

4,4,6-trimethyl-1,3-dioxan-2-ylmethyl bromide

1-(4,4,6-trimethyl-1,3-dioxan-2-yl)-1-bromoethane

1-(5,5-dimethyl-1,3-dioxan-2-yl)-1-bromoethane

1-(5,5-dimethyl-1,3-dioxan-2-yl)-2-bromoethane

1-(5,5-dimethyl-1,3-dioxan-2-yl)-2-bromopropane.

The above reactive acetals are a non-limitative selection. They can beprepared e.g. by reacting bromoacetaldehyde dimethyl or diethyl acetalswith 1,2-, 1,3-, 1,4- or 1,5-alkanediols, or 1,2-, 1,3-, 1,4- or1,5-alkanediols, which diols may be substituted by methyl, chloromethyl,C₁ -C₄ alkoxymethyl, C₂ -C₄ alkenyloxymethyl or nitro.

Examples of suitable diols, dimercaptans or mixed mercapto alcohols arethe following:

    ______________________________________                                        1,2-propanediol    (+) R--1,2-butanediol                                      (+) S--1,2-propanediol                                                                           (-) S--1,2-butanediol                                      (-) S--1,2-propanediol                                                                           1,2-butanediol                                             3-fluoro-1,2-propanediol                                                                         1,2-butanediol                                             3-chloro-1,2-propanediol                                                                         1,4-butanediol                                             3-bromo-1,2-propanediol                                                                          meso-2,3-butanediol                                        3-iodo-1,2-propanediol                                                                           (-)-2S,3S 2,3-butanediol                                   3-methoxy-1,3-propanediol                                                                        1-butene-2,3-diol                                          3-ethoxy-1,3-propanediol                                                                         2,3-pentanediol                                            3-isopropoxy-1,3-propanediol                                                                     2-methyl-1,2-butanediol                                    2-nitro-1,3-propanediol                                                                          2-methyl-2,3-butanediol                                    3-allyloxy-1,2-propanediol                                                                       2-methallyloxy-1,2-propane-                                                   diol                                                       3-propargyloxy-1,2-propanediol                                                                   3-acetoxy-1,3-propanediol                                  3-methylmercapto-1,2-propanediol                                                                 3-chloroallylmercapto-1,2-                                                    propanediol glycerol                                       ______________________________________                                    

1,3-propanediol

2-chloro-1,3-propanediol

2-bromo-1,3-propanediol

2-butene-1,4-diol

2-hydroxymethyl-2-propen-1-ol

2-hydroxymethyl-2-buten-1-ol

2-methyl-1,2-propanediol

3-chloro-2-methyl-1,2-propanediol

3-chloro-2-chloromethyl-1,2-propanediol

3-methyl-1,3-propanediol

2-methyl-2-nitro-1,3-propanediol

1,2-pentanediol

2,4-pentanediol

2-methyl-1,3-butanediol

2-methyl-2,4-butanediol

2-methyl-3,4-butanediol

1,4-dichloro-2-methyl-2,3-butanediol

4-iodo-2-methyl-2,3-butanediol

2,2-dimethyl-1,3-propanediol

2,4-hexanediol

3-methyl-2,4-pentanediol

1,5-hexane-3,4-diol

2-propanol-1-thiol

3-propanol-1-thiol

1,3-propane-dithiol

2,3-butane-dithiol

1-methyl-1,2-propane-dithiol

1-butene-2,3-dithiol

2-methyl-1,2-butanedithiol

2-ethyl-1,3-propanediol

4-bromo-2-methyl-2,3-butanediol

2,2-dimethyl-1,3-propanediol

2,2-bis-chloromethyl-1,3-propanediol

2-methyl-2,3-pentanediol

2,2-dimethyl-3,4-butanediol

2-ethanol-1-thiol

3-chloro-2-propanol-1-thiol

1,2-ethane-dithiol

1,2-butanedithiol

1,4-butenedithiol

2-butene-1,4-dithiol

2,3-pentane-dithiol

2-methyl-2,3-butanedithiol.

Compounds of the formula I can also be converted into other compounds. A4,7-dihydro-1,3-dioxepine compound of formula I is prepared e.g. by thefollowing reaction scheme: ##STR13##

According to a process described in Tetrahedron 21 (1980) 4922, thedouble bond is displaced by treating this compound at 100° C. with aruthenium catalyst to form the corresponding 4,5-dihydro-1,3-dioxepinecompound. ##STR14##

To prepare the compounds of formula I, wherein Y is an alkyl or phenylradical, the oxime salt of formula VI is reacted with a haloalkyl orphenyl ketal or thioketal, preferably with a bromo- or iodoketal, inaccordance with the reaction scheme: ##STR15##

Such haloketals are known from the literature. The α-bromacetone ketalcan be prepared by the method described in Synthesis 1982 309, and otherketals, e.g. 1-bromopinacoline ethylene ketal or 1-bromoacetophenoneethylene ketal, may be prepared by the method described in J. prakt.Chemie 156 (1940) 121.

These compounds can also be obtained by condensation of oximes e.g. withhaloketones such as bromacetone and subsequent ketalisation. A furthermethod of preparing such compounds is e.g. the reaction with2-methoxy-1,3-dioxolane as described in J. of Med.Chem. 25 (1982), 12,in accordance with the scheme: ##STR16##

The orthoesters of formula I (compounds in which Y is alkoxy) areprepared by reacting the oxime salt of formula VI with ahaloorthocarboxylic acid ester, e.g. triethyl monobromo-orthoacetate, inaccordance with J.Am.Soc.59 (1937), 1273 and with the reaction scheme:##STR17##

Reaction of the halo-orthocarboxylates with suitable diols andmercaptans gives mixed esters such as glycol ethyl bromo-orthoacetate ordimethylthioethyl bromo-orthoacetate, which are suitable for reactionwith the oxime salt of formula VI. Orthoesters of formula I can also beprepared e.g. by a method described in J.Am.Chem.Soc.77 (1955), 4574, byreacting a cyanoalkyl oxime to give the iminoester hydrochloride andsubsequently condensing this latter compound with a diol, e.g. glycol,according to the reaction scheme: ##STR18##

Compounds of formula I, wherein A and/or B are sulfur, are prepared bymethods similar to those employed for preparing the acetal compounds.Simple thioacetals, thioketals, dithiolanes and dithianes can beprepared by using thiols or dithiols. Particularly suitable, however, isthe transesterification of aliphatic dialkyl acetals e.g. with amercaptan, e.g. the transesterification of an oxime dimethoxyethylesterwith a mercaptan such as 1,2-ethylenedithiol in the following reactionscheme: ##STR19##

These same cyclic thioacetal compounds can also be obtained by reactingthe corresponding acetals with dithiols according to the reactionscheme: ##STR20##

Compounds of formula I, wherein A is oxygen, B is methylene and Y ishydrogen, and R₅ and R₆ together form a hydrocarbon bridge member, canbe prepared by reacting the oxime salts of formula VI with corresponding2-α-haloalkyl oxygen rings such as 2-bromomethylfurane,2-bromomethylpyrane, 2-bromoethyloxepane, according to the reactionscheme: ##STR21##

Instead of starting from oxime salts of formula VI as in the precedingprocesses, it is also possible to start from the ketones on which theseoximes are based and reacting them with O-substituted hydroxylamines inaccordance with the reaction scheme: ##STR22##

Further, such phenones can be transacetalised with correspondinglysubstituted acetone oxime ethers to give compounds of the formula I##STR23##

The novel oxime ethers of formula I are most suitable for protectingcultivated plants from damage caused by agrochemicals. This protectionextends in particular to herbicides of different compound classes,including 1,3,5-triazines, 1,2,4-triazines, phenylurea derivatives,carbamates, thiocarbamates, phenoxyacetates, phenoxypropionates,haloacetanilides, halophenoxyacetates, substitutedphenoxyphenoxyacetates and phenoxyphenoxypropionates, substitutedpyridyloxyphenoxyacetates and pyridyloxyphenoxypropionates, benzoic acidderivatives etc., where these compounds are not tolerated or areinsufficiently tolerated by cultivated plants. The novel oxime ethers offormula I are suitable in particular for protecting cultivated plantsfrom the harmful effects of haloacetanilides and thiocarbamates. Theycan therefore be termed antidotes or also safeners with respect to theiruse in combination with the herbicides referred to above.

The compounds of the formula I exist in different isomeric forms. Asoxime derivatives, these compounds are obtained in the syn- andanti-form or as mixtures thereof (E- and Z-form, cf. R. S. Cohn et al.,Ang. Chemie Int. Ed. 5 (1966), 385, or Experientia 12 (1956), p. 81).

Depending on the substitution of the compounds of formula I, anasymmetrical carbon atom is present and two enantiomers may be obtained.In general, a mixture of both enantiomers is obtained, which mixture canbe resolved into the optional antipodes in conventional manner.

The monosubstituted dioxolanes and dioxanes lead to furthercis-trans-isomers or mixtures thereof. Disubstituted dioxolanes lead tocis-syn-isomers, cis-anti-isomers and to trans-isomers or mixturesthereof. The number of isomers can be reduced by choice of startingmaterials, e.g. by using the pure Z-form of the oximes. The presentinvention also relates to these different isomers and to mixturesthereof.

Depending on the end use, the safener or antidote of the formula I canbe used for pretreating seeds of the cultivated plant (dressing of theseeds or seedlings) or it can be added to the soil before or aftersowing. However, it can also be applied pre- or post-emergence by itselfalone or together with the herbicide. The treatment of the plant orseeds with the antidote can therefore in principle be carried outindependently of the time of application of the phytotoxic chemical. Itcan, however, also be carried out by simultaneous application ofphytoxic chemical and antidote (tank mixture). The pre-emergencetreatment includes both treatment of the crop area before sowing(ppi=pre-plant incorporation) and treatment of the crop areas aftersowing but before emergence of the plants.

The rates of application of the antidote with respect to the herbicidedepend largely on the mode of application. Where a field treatment iscarried out, either simultaneously as tank mixture or with separateapplication of herbicide and antidote, the ratio of antidote toherbicide is in the range from 1:100 to 5:1. Full protective action isusually obtained at a ratio of antidote to herbicide of 1:1 to 1:20.When dressing seeds and taking similar specific protective measures,however, much lower amounts of antidote are required compared with e.g.the amounts of herbicide later employed per hectare or crop area. Forseed dressing, 0.1 to 10 g of antidote per kg of seeds are required,with the preferred amount being from 1 to 2 grams. If it is desired toapply the antidote shortly before sowing by seed pretreatment, antidotesolutions which contain the active ingredient in a concentration of 1 to10,000 ppm are used. Full protective action is normally obtained withantidote concentrations of 100 to 1000 ppm.

As a rule there is a substantial interval of time between protectivemeasures such as seed dressing and treatment of seedlings with anantidote of the formula I and the possible later field treatment withagricultural chemicals. Pretreated seeds and plants can later come incontact with different chemicals in agriculture, horticulture andforestry. Accordingly, the invention relates to plant protectioncompositions which contain an antidote of the formula I as activeingredient, together with conventional carriers. If appropriate, suchcompositions may be additionally mixed with the chemical against whoseeffects it is desired to protect the cultivated plant.

Cultivated plants within the scope of this invention are all plantswhich, in any form, can be harvested (seeds, roots, stalks, tubers,leaves, blossoms) and from which extracts can be obtained (oils, sugar,starch, protein) and which are cultivated for this purpose.

To these plants belong e.g. all species of cereals such es wheat, rye,barley, oats and, in particular, rice, sorghum, maize, and also cotton,sugar beet, sugar cane, soybeans, beans, and peas.

The antidote can be employed wherever it is desired to protect acultivated plant of the kind indicated above from the harmful effects ofan agricultural chemical. As already mentioned, possible agriculturalchemicals are primilarly herbicides of the most widely varying compoundclasses, in particular haloacetanilides and thiocarbamates.

Numerous haloacetanilides whose harmful effects on cultivated plants canbe antagonised with the novel oxime ethers of the formula I are known inthe art (q.v. German patent applications 2 305 495, 2 328 340, 2 212268, 2 726 252 and 2 805 757, and U.S. Pat. Nos. 3,946,044, 4,022,608and 4,039,314). Such haloacetanilides may be illustrated by the generalformula XIV ##STR24## wherein Hal is halogen, preferably chlorine orbromine, each of R₈ and R₉ independently of the other is hydrogen,halogen, lower alkyl, alkoxy, alkylthio, haloalkyl, alkoxyalkyl oralkylthioalkyl, Z is hydrogen, halogen, lower alkyl, alkoxy, alkylthio,haloalkyl, alkoxyalkyl or alkylthioalkyl, which radicals Z arepreferably in the 3-position with respect to the nitrogen atom, n is 0to 3, A is alkylene, preferably methylene, 1,1-ethylene, and1,2-ethylene which may be substituted by 1 or 2 lower alkyl groups, andR₁₀ is lower alkoxy, hydroxycarbonyl, alkoxycarbonyl, carbamoyl,N-alkylcarbamoyl, N,N-dialkylcarbamoyl, cyano, an unsubstituted orsubstituted nitrogen-containing heterocyclic radical, alkanoyl,unsubstituted or substituted benzoyl, unsubstituted or substituted1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-3-yl or1,3,4-triazol-1-yl.

Typical examples of such haloacetanilides are:

N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2,6-dimethylaniline

N-(2-allyloxyethyl)-N-chloroacetyl-2,6-dimethylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-isopropoxyethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(methoxyethyl)-2,6-diethylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-methylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline

N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methylaniline

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline

N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methylaniline

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-methoxycarbonylmethyl-2,6-dimethylaniline

N-chloroacetyl-N-(2,2-diethoxyethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,3-dimethylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2-methylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2-methylaniline

N-chloroacetyl-N-(2-methoxy-2-methylethyl)-2,6-dimethylaniline

N-(2-ethoxy-2-methylethyl)-N-chloroacetyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1-ethyl-2-methoxyethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2-methoxy-6-methylaniline

N-n-butoxymethyl-N-chloroacetyl-2-tert-butylaniline

N-(2-ethoxyethyl-1-methylethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2-chloro-6-methylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2-chloro-6-methylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2,3,6-trimethylaniline

N-chloroacetyl-1-(2-methoxyethyl)-2,3,6-trimethylaniline

N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline

N-but-3-yn-1-yl-N-chloroacetylaniline

N-chloroacetyl-N-propargyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-furanylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-furanylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-tetrahydrofuranylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(N-propargylcarbamoylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(N,N-dimethylcarbamoylmethyl)-2,6-dimethylaniline

N-(n-butoxymethyl)-N-chloroacetyl-2,6-diethylaniline

N-(2-n-butoxyethyl)-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxy-1,2-dimethylethyl)-2,6-dimethylaniline

N-chloroacetyl-N-isopropyl-2,3-dimethylaniline

N-chloroacetyl-N-isopropyl-2-chloroaniline

N-chloroacetyl-N-(1H-pyrazol-1-ylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(1H-pyrazol-1-ylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1H-1,2,4-triazol-1-ylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(1H-1,2,4-triazol-1-ylmethyl)-2,6-diethylaniline

N-benzoylmethyl-N-chloroacetyl-2,6-dimethylaniline

N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2,6-diethylaniline

N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-tert-butylaniline

N-chloroacetyl-N-(4-chlorobenzoylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(1-methyl-5-methylthio-1,3,4-triazol-2-ylmethyl)-2,6-diethylaniline.

Further haloacetanilides whose harmful effects on cultivated plants canbe antagonised by the novel oxime ethers of the formula I are listed inR. Wegler, Chemie der Pflanzenschutz- und Schadlingsbekaampfungsmittel,Vol. 8, pp. 90-93 and pp. 322-327.

Numerous herbicidal thiocarbamates whose phytotoxic action on cultivatedplants can be antagonised by the novel oxime ethers of the formula I arealso known (q.v. for example U.S. Pat. Nos. 2,913,327, 3,037,853,3,175,897, 3,185,720, 3,198,786, 3,582,314 and 3,846,115). Theprotective action of the novel oxime ethers of the formula I can beutilised particularly when applying thiocarbamates in cereals, rice orsorghum.

The thiocarbamates against whose phytotoxic action cultivated plantssuch as cereals, rice and sorghum may particularly be protected, havethe general formulae XV and XVI: ##STR25## wherein R₁₁ is lower alkyl,alkenyl, chloroallyl, dichloroallyl, trichloroallyl, benzyl or4-chlorobenzyl, R₁₂ is C₂ -C₄ alkyl and R₁₃ is C₂ -C₄ alkyl orcyclohexyl, and R₁₂ and R₁₃ together with the nitrogen atom to whichthey are attached can form a hexahydro-1H-azepine, decahydroquinoline or2-methyldecahydroquinoline ring.

Typical individual representatives of such thiocarbamates are:

S-ethyl-N,N-dipriopylthiocarbamate

S-ethyl-N,N-diisobutylthiocarbamate

S-2,3-dichloroallyl-N,N-diisopropylthiocarbamate

S-propyl-N-butyl-N-ethylthiocarbamate

S-2,3,3-trichloroallyl-N,N-diisopropylthiocarbamate

S-propyl-N,N-dipropylthiocarbamate

S-ethyl-N-ethyl-N-cyclohexylthiocarbamate

S-ethyl-N-hexahydro-1H-azepine-1-carbothioate

S-isopropyl-N,N-hexamethylene-thiocarbamate

S-(p-chlorobenzyl)-N,N-diethylthiocarbamate

N-ethylthiocarbonyl-cis-decahydroquinoline

N-propylthiocarbonyl-decahydroquinaldine

S-ethyl-N,N-bis(n-butyl)-thiocarbamate

S-tert-butyl-N,N-bis(n-propyl)-thiocarbamate.

In addition to the chloroacetanilides and thiocarbamates, herbicides ofother compound classes are also possible, e.g.:

Triazines and triazinones:2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine ("prometryn"),2,4-bis(ethylamino)-6-methylthio-1,3,5-triazine ("symetryn"),2-(1',2'-dimethylpropylamino)-4-ethylamino-6-methylthio-1,3,5-triazine("dimethametryn"),4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one("metribuzin"),2-tert-butylamino-4-ethylamino-6-methylthio-1,3,5-triazine("terbutryn"), 2-chloro-4-tert-butylamino-6-ethylamino-1,3,5-triazine("terbuthylazin"), 2-chloro-4-isopropylamino-6-ethylamino-1,3,5-triazine("atrazin"), 2-tert-butylamino-4-alkylamino-6-methoxy-1,3,5-triazine("terbumeton"), 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine ("simazin"),2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine ("ametryn").

Ureas: 1-(benzothiazol-2-yl)-1,3-dimethylurea; phenylureas such as3-(3-chloro-p-tolyl)-1,1-dimethylurea ("chlortoluron"),1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea ("fluometuron"),3-(4-bromo-3-chlorophenyl)-1-methoxy-1-methylurea ("chlorbromuron"),3-(4-bromophenyl)-1-methoxy-1-methylurea ("metobromuron"),3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea ("linuron"),3-(4-chlorophenyl)-1-methoxy-1-methylurea ("monolinuron"),3-(3,4-dichlorophenyl)-1,1-dimethylurea ("diuron"),3-(4-chlorophenyl)-1,1-dimethylurea ("monuron"),3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea ("metoxuron");sulfonylureas such asN-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea,N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethylpyrimidin-2-yl)urea,N-[2-(2-butenyloxy)phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea,as well as the sulfonylureas cited in European patent publication Nos.44808 and 44809.

Chloroacetamides:N-[1-isopropyl-2-methylpropan-1-yl(1)]-N-(2'-methoxyethyl)-chloroacetamide

Diphenyl ethers and nitrodiphenyl ethers:2,4-dichlorophenyl-4'-nitrophenyl ether ("nitrofen"),2-chloro-1-(3'-ethoxy-4'-nitrophenoxy)-4-trifluoromethylbenzene("oxyfluorfen"), 2',4'-dichlorophenyl-3-methoxy-4-nitrophenyl ether("chlormethoxynyl"), methyl2-[4'-(2",4"-dichlorophenoxy)phenoxy]propionate,N-(2'-phenoxyethyl)-2-[5'(2"-chloro-4"-trifluoromethylphenoxy)-phenoxy]propionamide,2-methoxyethyl2-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenoxy]propionate,2-chloro-4-trifluoromethylphenyl-3'-oxazolin-2'-yl-4'-nitrophenyl ether.

Benzoic acid derivatives:methyl-5-(2',4'-dichlorophenoxy)-2-nitrobenzoate ("bifenox"),5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitrobenzoic acid("acifluorfen"), 2,6-dichlorobenzonitrile ("dichlobenil").

Nitroanilines: 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline("trifluralin"), N(1'-ethylpropyl)-2,6-dinitro-3,4-xylidine("pendimethalin").

Oxadiazolones:5-tert-butyl-3(2',4'-dichloro-5'-isopropoxyphenyl)-1,3,4-oxadiazol-2-one("oxadiazon").

Phosphates:S-2-methylpiperidinocarbonylmethyl-O,O-dipropylphosphorodithioate("piperophos").

Pyrazoles:1,3-dimethyl-4-(2',4'-dichlorobenzoyl)-5-(4'-tolylsulfonyloxy)pyrazole.

α-(Phenoxyphenoxy)propionic acid derivatives andα-Pyridyl-2-oxyphenoxy)propionic acid derivatives

The amount of antidote employed varies from about 0.01 to about 15 partsby weight per part by weight of herbicide. The most suitable ratio inrespect of optimum action on the particular cultivated plant isestablished from case to case, i.e. depending on the type of herbicideemployed.

The compounds of the formula I are used in unmodified form or,preferably, together with the adjuvants conventionally employed in theart of formulation, and are therefore formulated in known manner toemulsifiable concentrates, coatable pastes, directly sprayable ordilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts, granulates, and also encapsulations in e.g. polymersubstances. As with the nature of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering orpouring, are chosen in accordance with the intended objectives and theprevailing circumstances.

The formulations, i.e. the compositions containing the compound (activeingredient) of the formula I and, where appropriate, a solid or liquidadjuvant, are prepared in known manner, e.g. by homogeneously mixingand/or grinding the active ingredients with extenders, e.g. solvents,solid carriers and, where appropriate, surface-active compounds(surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycolmonomethyl or monoethyl ether, ketones such as cyclohexanone, stronglypolar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide ordimethylformamide, as well as epoxidsed vegetable oils such asepoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. In addition, a great number of pregranulated materialsof inorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of the formula I to beformulated, suitable surface-active compounds are nonionic, cationicand/or anionic surfactants having good emulsifying, dispersing andwetting properties. The term "surfactants" will also be understood ascomprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained e.g. from coconutoil or tallow oil. Mention may also be made of fatty acid methyltaurinsalts.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metalsalts, alkaline earth metal salts or unsubstituted or substitutedammoniums salts and contain a C₈ -C₂₂ alkyl radical which also includesthe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt oflignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcoholsulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfuric acid esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and one fatty acid radicalcontaining 8 to 22 carbon atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid,dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonicacid/formaldehyde condensation product. Also suitable are correspondingphosphates, e.g. salts of the phosphoric acid ester of an adduct ofp-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphtic or cycloaliphatic alcohols, or saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol, ethylenediamine propyleneglycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms inthe alkyl chain, which adducts contain 20 to 250 ethylene glycol ethergroups and 10 to 100 propylene glycol ether groups. These compoundsusually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitanand polyoxyethylene sorbitan trioleate are also suitable non-ionicsurfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, lower unsubstituted or halogenated alkyl, benzylor lower hydroxyalkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniumchloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation aredescribed e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MCPublishing Corp. Ringwood, N.J., 1979, and Sisely and Wood,"Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc.New York, 1980.

These compositions usually contain 0.1 to 99%, preferably 0.1 to 95%, ofa compound of the formula I, 1 to 99% of a solid or liquid adjuvant, and0 to 25%, preferably 0.1 to 25%, or a surfactant.

Whereas commercial products are preferably formulated as concentrates,the end user will normally employ dilute formulations.

The compositions may also contain further ingredients, such asstabilisers, antifoams, viscotity regulators, binders, tackifiers aswell as fertilisers or other active ingredients in order to obtainspecial effects.

The invention is illustrated in more detail by the following Examples,without implying any restriction to what is described therein. Parts andpercentages are by weight.

EXAMPLE 1 Preparation of1-(4-chlorophenyl)-1-(1,3-dioxolan-2-ylmethoxyimino)-2,2,2-trifluoroethane(compound 40)

(a) In a 100 ml round flask, 1.2 g (0.05 mole) of metallic sodium aredissolved in 50 ml of absoute ethanol, and then 11.2 g (0.05 mole) of1-(4-chlorophenyl)-1-hydroximino-2,2,2-trifluoroethane are added. Whenthe addition is complete, the reaction mixture is stirred initially forhalf an hour at room temperature and then the solvent is removed byevaporation. With stirring, 8.4 g (0.05 mole) of2-bromomethyl-1,3-dioxolane are added dropwise to the solution of theresidue in 50 ml of dimethylsulfoxide and the batch is subsequentlystirred for 4 hours at 60° to 70° C. The resultant suspension is cooledand poured into a mixture of ice and water. The reaction product isobtained from the mixture by extraction with methylene chloride. Theextract is dried over sodium sulfate and the solvent is removed byevaporation. The crude product is an orange oil which is purified bydistillation in a high vacuum. Yield: 12.5 g (80.6% of theory) of1-(4-chlorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethanein the form of a colourless oil with a boiling point of 105° to 108°C./0.1 mbar.

(b) The starting 1-(4-chlorophenyl)-hydroximino-2,2,2-trifluoroethane isprepared as follows:

A mixture of 417 g (2 moles) of 4-chloro-ω,ω,ω-trifluoroacetophenone,139 g (2 moles) of hydroxylamino hydrochloride and 500 ml of pyridine isstirred for 15 hours at room temperature. The pyridine is subsequentlyremoved by distillation and the oily residue is stirred in ice/water.The product is extracted with methylene chloride and extract is driedover sodium sulfate and the solvent removed by evaporation, affording438 g (98% of theory) of1-(4-chlorophenyl)-1-hydroximino-2,2,2-trifluoroethane in the form of anoil.

EXAMPLE 2 Preparation of1-phenyl-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane(compound 38)

13.8 (0.07 mole) of 1-(hydroximino)-1-phenyl-2,2,2-trifluoroethane arestirred into a solution of 1.5 g (0.07 mole) of metallic sodium in 50 mlof absolute ethanol and the solvent is subsequently evaporated off. Withstirring, 6.7 g (0.10 mole) of 2-bromomethyl-1,3-dioxolane are addeddropwise to the solution of the residue in 50 ml of dimethylsulfoxide.When the addition of 2-bromomethyl-1,3-dioxolane is complete, thereaction mixture is stirred initially for 4 hours at 60° to 70° C. andthen the resultant suspension is poured into a mixture of ice and water.The product is extracted with methylene chloride and the extract isdried over sodium sulfate and the solvent is removed by evaporation. Thecrude product is an orange oil which is purified by distillation in ahigh vacuum. Yield: 15 g (78% of theory) of1-phenyl-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane with aboiling point of 89° to 90° C./0.1 mbar.

EXAMPLE 3 Preparation of1-(4-chlorophenyl)-1-(2,2-diethoxyethoximino)-2,2,2-trifluoroethane(compound 11)

25.6 g (0.1 mole) of1-hydroximino-1-(4-chlorophenyl)-2,2,2-trifluoroethane are addeddropwise to a solution of 2.3 g (0.1 mole) of metallic sodium in 50 mlof absolute ethanol. When the addition is complete, the reaction mixtureis stirred for half an hour at room temperature and then the solvent isremoved by evaporation. With stirring, 29.7 g (0.15 mole) of2-bromacetaldehyde diethyl acetal are added to the solution of theresidue in 50 ml of dimethylsulfoxide. When the addition is complete,the reaction mixture is stirred for 4 hours at 60° to 70° C. and thenpoured into a mixture of ice and water. The crude oily product obtainedafter extraction with methylene chloride, drying the extract over sodiumsulfate and removing the solvent by evaporation is purified bydistillation in a high vacuum. Yield: 20.5g (73.5% of theory) of1-(4-chlorophenyl)-1-(2,2-diethoxyethoximino)-2,2,2-trifluoroethane inthe form of a colourless oil with a boiling point of 95° to 97° C./0.02mbar.

EXAMPLE 4 Preparation of1-(4-chlorophenyl)-1-(2,2-dimethoxyethoximino)-2,2,2-trifluoroethane(compound 2)

25.6 g (0.1 mole) of1-hydroximino-1-(4-chlorophenyl)-2,2,2-trifluoroethane are addeddropwise to a solution of 2.3 g (0.1 mole) of metallic sodium in 50 mlof absolute ethanol. When the addition is complete, the reaction mixtureis stirred for half an hour at room temperature and then the solvent isremoved by evaporation. With stirring, a solution of 33.8 g (0.2 mole)of 2-bromoacetaldehyde demethyl acetal in 60 ml of dimethylsulfoxide areadded to the solution of the residue in 50 ml of dimethylsulfoxide. Whenthe addition is complete, the reaction mixture is stirred for 4 hours at60° to 70° C., then cooled and poured into a mixture of ice and water.The crude oily product obtained after extraction with methylenechloride, drying the extract over sodium sulfate and removing thesolvent by evaporation is purified by distillation in a high vacuum.Yield: 22 g (70.5% of theory) of1-(4-chlorophenyl)-1-(2,2,-dimethoxyethoximino)-2,2,2-trifluoroethane inthe form of a colourless oil with a boiling point of 96° to 98° C./0.02mbar.

The following compounds are prepared in accordance with the precedingExamples

                                      TABLE 1                                     __________________________________________________________________________                                                   Physical                       No.                                                                              X   n R.sub.1                                                                           R.sub.2                                                                            R.sub.3                                                                              R.sub.4                                                                           R.sub.5  R.sub.6  data (°C.)              __________________________________________________________________________     ##STR26##                                                                    1  CF.sub.3                                                                          1 H   H    H      H   CH.sub.3 CH.sub.3 b.p. 66-68°/                                                           0.03 mbar                      2  CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.3 CH.sub.3 b.p. 96-98°/                                                           0.02 mbar                      3  CF.sub.3                                                                          1 H   H    H      H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        b.p. 77-78°/                                                           0.04 mbar                      4  CF.sub.3                                                                          1 H   H    4-F    H   CH.sub.3 CH.sub.3 b.p. 67-68°/                                                           0.01 mbar                      5  CF.sub.3                                                                          1 H   H    4-Cl   H   n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                       6  CClF.sub.2                                                                        1 H   H    4-OCH.sub.3                                                                          H   n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                       7  CClF.sub.2                                                                        2 H   H    H      H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         8  CF.sub.3                                                                          1 CH.sub.3                                                                          H    3-NO.sub.2                                                                           H   CH.sub.3 CH.sub.3                                9  C.sub.2 F.sub.5                                                                   1 CH.sub.3                                                                          3-Cl 4-Cl   H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         10 CClF.sub.2                                                                        1 CH.sub.3                                                                          H    2-Cl   H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         11 CF.sub.3                                                                          1 H   H    4-Cl   H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        b.p. 95-97°/                                                           0.02 mbar                      12 CF.sub.3                                                                          1 CH.sub.3                                                                          H    3-NO.sub.2                                                                           H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         13 C.sub.2 F.sub.5                                                                   1 CH.sub.3                                                                          H    4-OCH.sub.3                                                                          H   CH.sub.3 CH.sub.3                                14 C.sub.2 F.sub.5                                                                   1 CH.sub.3                                                                          H    4-OCF.sub.3                                                                          H   i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                       15 CF.sub.3                                                                          1 H   H    2-Cl   H   i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                       16 CF.sub.3                                                                          1 CH.sub.3                                                                          H    H      H   CH.sub.2CHCH.sub.2                                                                     CH.sub.2CHCH.sub.2                      17 C.sub.2 F.sub.5                                                                   1 H   H    4-Cl   H   CH.sub.3 CH.sub.3                                18 CF.sub.3                                                                          1 H   H    4-OCH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         19 CF.sub.3                                                                          1 H   H    4-OCF.sub.3                                                                          H   n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                       20 CF.sub.3                                                                          1 CH.sub.3                                                                          H    4-SO.sub.2CF.sub.3                                                                   H   CH.sub.3 CH.sub.3                                21 CClF.sub.2                                                                        1 H   H    4-Cl   H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         22 CF.sub.3                                                                          1 CH.sub.3                                                                          H    3-CF.sub.3                                                                           H   CH.sub.3 CH.sub.3                                23 C.sub.2 F.sub.5                                                                   1 H   H    4-OCH.sub.3                                                                          H   CH.sub.2CHCH.sub.2                                                                     CH.sub.2CHCH.sub.2                      24 C.sub.3 C.sub.7                                                                   1 H   H    4-Cl   H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         25 CF.sub.3                                                                          1 CH.sub.3                                                                          H    3-CF.sub.3                                                                           H   n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                       26 CF.sub.3                                                                          1 C.sub.2 H.sub.5                                                                   H    3-NO.sub. 2                                                                          H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         27 CF.sub.3                                                                          2 H   H    2-F    H   CH.sub.3 CH.sub.3                                28 CF.sub.3                                                                          1 i-C.sub.3 H.sub.7                                                                 H    2-Cl   H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         29 CF.sub.3                                                                          2 CH.sub.3                                                                          H    3-CF.sub.3                                                                           H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         30 CF.sub.3                                                                          1 H   H    3-NO.sub.2                                                                           H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         31 CF.sub.3                                                                          1 H   H    4-OCH.sub.3                                                                          H   CH.sub.2CHCH.sub.2                                                                     CHCHCH.sub.2                            32 CF.sub.3                                                                          1 H   H    4-SO.sub.2 CF.sub.3                                                                  H   CH.sub.3 CH.sub.3                                33 C.sub.2 F.sub.5                                                                   1 H   H    3-CF.sub.3                                                                           H                                                                                  ##STR27##                                                                              ##STR28##                              34 CF.sub.3                                                                          1 H        4-Cl   H   CH.sub.2CHCH.sub.2                                                                     CH.sub.2CHCH.sub.2                      35 C.sub.2 F.sub.5                                                                   1 H   H    4-Cl   H   CH.sub.3 CH.sub.3                                36 C.sub.2 F.sub.5                                                                   1 H   H    H      H   CH.sub.2CHCH.sub.2                                                                     CH.sub.2CHCH.sub.2                      37 CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CHCH.sub.2                                                                     CH.sub.2CHCH.sub.2                      38 CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2  b.p. 89-90°/                                                           0.1 mbar                       39 CF.sub.3                                                                          2 H   H    H      H   CH.sub.2CH.sub.2  b.p. 92-93°/                                                           0.03 mbar                      40 CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2  b.p. 105-                                                                     108°/                                                                  0.1 mbar                       41 CF.sub.3                                                                          1 H   H    4-F    H   CH.sub.2CH.sub.2  b.p. 77-78°/                                                           0.02 mbar                      42 CF.sub.3                                                                          2 H   H    4-F    H   CH.sub.2CH.sub.2  b.p. 78-79°/                                                           0.15 mbar                      43 CF.sub.3                                                                          1 H   H    H      H                                                                                  ##STR29##        b.p 77-78°/ 0.05                                                       mbar                           44 CF.sub.3                                                                          1 H   H    H      H                                                                                  ##STR30##        b.p. 82-83° 0.07                                                       mbar                           45 CF.sub.3                                                                          1 H   H    4-Cl   H                                                                                  ##STR31##                                       46 CClF.sub.2                                                                        1 H   H    4-OCH.sub.3                                                                          H                                                                                  ##STR32##                                       47 CF.sub.3                                                                          1 H   3-Cl 4-Cl   H   CH.sub.2CH.sub.2                                 48 CClF.sub.2                                                                        1 H   H    H      H   CH.sub.2CH.sub.2                                 49 C.sub.2 F.sub.5                                                                   1 H   H    4-OCF.sub.3                                                                          H   CH.sub.2CH.sub.2                                 50 CF.sub.3                                                                          1 H   H    4-OCF.sub.3                                                                          H   CH.sub.2CH.sub.2                                 51 CF.sub.3                                                                          1 H   H    3-CF.sub.3                                                                           H                                                                                  ##STR33##                                       52 CF.sub.3                                                                          1 H   H    4-OCH.sub.3                                                                          H   CH.sub.2CH.sub.2                                 53 CF.sub.3                                                                          1 H   H    3-NO.sub.2                                                                           H                                                                                  ##STR34##                                       54 CClF.sub.2                                                                        1 CH.sub.3                                                                          H    2-F    H   CH.sub.2CH.sub.2                                 55 C.sub.2 F.sub.5                                                                   1 CH.sub.3                                                                          H    2-F    H   CH.sub.2CH.sub.2                                 56 CClF.sub.2                                                                        1 CH.sub.3                                                                          H    2-F    H                                                                                  ##STR35##                                       57 CF.sub.3                                                                          1 H   2-Cl 4-Cl   H   CH.sub.2CH.sub.2                                 58 CF.sub.3                                                                          1 H   2-Cl 4-Cl   5-NO.sub.2                                                                        CH.sub.2CH.sub.2                                 59 CF.sub.3                                                                          1 H   3-CH.sub.3                                                                         4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2                                 60 CClF.sub.2                                                                        1 CH.sub.3                                                                          3-CH.sub.3                                                                         4-Cl   H   CH.sub.2CH.sub.2                                 61 CF.sub.3                                                                          1 CH.sub.3                                                                          2-Cl 4-Cl   5-CF.sub.3                                                                        CH.sub.2CH.sub.2                                 62 CF.sub.3                                                                          1 H   2-F  4-F    5-NO.sub.2                                                                        CH.sub.2CH.sub.2                                 63 CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2CH.sub.2                                                                        b.p. 82-83°                                                            0.04 mbar                      64 CF.sub.3                                                                          2 H   H    H      H   CH.sub.2CH.sub.2CH.sub.2                         65 CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2CH.sub.2                                                                        b.p 96-98°                                                             0.08 mbar                      66 CF.sub.3                                                                          1 H   H    4-F    H   CH.sub.2CH.sub.2CH.sub.2                                                                        b.p. 87-89°                                                            0.04 mbar                      67 CF.sub.3                                                                          1 H   H    H      H                                                                                  ##STR36##                                       68 C.sub.2 F.sub.5                                                                   1 H   H    4-OCF.sub.3                                                                          H                                                                                  ##STR37##                                       69 CClF.sub.2                                                                        1 H   H    4-OCH.sub.3                                                                          H                                                                                  ##STR38##                                       70 CClF.sub.2                                                                        1 H   H    4-Cl   H                                                                                  ##STR39##                                       71 CF.sub.3                                                                          1 CH.sub.3                                                                          H    3-NO.sub.2                                                                           H   CH.sub.2CH.sub.2CH.sub.2                         72 CF.sub.3                                                                          1 CH.sub.3                                                                          H    3-CF.sub.3                                                                           H    CH.sub.2CH.sub.2CH.sub.2                        73 CF.sub.3                                                                          1 CH.sub.3                                                                          3-Cl 4-Cl   H   CH.sub.2CH.sub.2CH.sub.2                         74 CF.sub.3                                                                          1 H   3-CH.sub.3                                                                         4-CH.sub.3                                                                           H                                                                                  ##STR40##                                       75 C.sub.2 F.sub.5                                                                   1 H   3-Cl 4-Cl   H   CH.sub.2CH.sub.2CH.sub.2                         76 C.sub.3 F.sub.7                                                                   1 H   H    H      H   CH.sub.2CH.sub.2CH.sub.2                         77 CF.sub.3                                                                          1 CH.sub.3                                                                          H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2CH.sub.2                         78 CF.sub.3                                                                          1 H   2-Cl 4-Cl   5-NO.sub.2                                                                        CH.sub.2CH.sub.2CH.sub.2                         79 CF.sub.3                                                                          1 CH.sub.3                                                                          2-Cl 4-Cl   5-CF.sub.3                                                                        CH.sub.2CH.sub.2CH.sub.2                         80 CClF.sub.2                                                                        1 CH.sub.3                                                                          H    H      H   CH.sub.2CH.sub.2CH.sub.2                         81 CF.sub.3                                                                          2 CH.sub.3                                                                          H    4-Cl   H                                                                                  ##STR41##                                       82 C.sub.2 F.sub.5                                                                   2 H   H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2CH.sub.2                         83 CF.sub.3                                                                          2 H   3-Cl 4-Cl   H   CH.sub.2CH.sub.2CH.sub.2                         84 CF.sub.3                                                                          1 CH.sub.3                                                                          3-NO.sub.2                                                                         4-Cl   H   CH.sub.2CH.sub.2CH.sub.2                         85 CF.sub.3                                                                          1 CH.sub.3                                                                          H    3-NO.sub.2                                                                           H                                                                                  ##STR42##                                       86 CF.sub.3                                                                          1 H   H    2-Cl   H   CH.sub.2CH.sub.2CH.sub.2                         87 CF.sub.3                                                                          1 H   H    2-F    H                                                                                  ##STR43##                                       88 CClF.sub.2                                                                        1 H   H    4-OCF.sub.3                                                                          H   CH.sub.2CH.sub.2CH.sub.2                         89 CF.sub.3                                                                          1 H        4-SO.sub.2 CF.sub.3                                                                  H   CH.sub.2CH.sub.2CH.sub.2                         90 CF.sub.3                                                                          1 H   H    4-Cl   H   CH(CH.sub.3)CH.sub.2CH(CH.sub.3)                                                                b.p. 104-5°/                                                           0.04 mbar                      91 CF.sub.3                                                                          2 H   H    3-CF.sub.3                                                                           H   CH.sub.2 CH.sub.2                                92 CF.sub.3                                                                          1 H   H    3-CF.sub.3                                                                           H   CH.sub.3 CH.sub.3                                93 CF.sub.3                                                                          1 H   H    3-CF.sub.3                                                                           H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         94 C.sub.2 F.sub.5                                                                   1 H   H    H      H   CH.sub.3 CH.sub.3                                95 C.sub.2 F.sub.5                                                                   1 H   H    H      H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         96 C.sub.2 F.sub.5                                                                   1 H   H    H      H   CH.sub.2CH.sub.2  b.p. 128-130°                                                          0.1 mbar                       97 C.sub.2 F.sub.5                                                                   2 H   H    H      H   CH.sub.2CH.sub.2                                 98 C.sub.2 F.sub.5                                                                   1 H   H    4-Cl   H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         99 C.sub.2 F.sub.5                                                                   1 H   H    4-Cl   H   CH.sub.2CH.sub.2                                 100                                                                              C.sub.2 F.sub.5                                                                   2 H   H    4-Cl   H   CH.sub.2CH.sub.2                                 101                                                                              C.sub.2 F.sub.5                                                                   1 H   H    4-F    H   CH.sub.3 CH.sub.3                                102                                                                              C.sub.2 F.sub.5                                                                   1 H   H    4-F    H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         103                                                                              C.sub.2 F.sub.5                                                                   1 H   H    4-F    H   CH.sub.2CH.sub.2                                 104                                                                              C.sub.2 F.sub.5                                                                   2 H   H    4-F    H   CH.sub.2CH.sub.2                                 105                                                                              C.sub.2 F.sub.5                                                                   1 H   H    2-F    H   CH.sub.3 CH.sub.3                                106                                                                              C.sub.2 F.sub.5                                                                   1 H   H    2-F    H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         107                                                                              C.sub.2 F.sub.5                                                                   1 H   H    2-F    H   CH.sub.2CH.sub.2                                 108                                                                              C.sub.2 F.sub.5                                                                   2 H   H    2-F    H   CH.sub.2CH.sub.2                                 109                                                                              CF.sub.3                                                                          1 H   H    2-F    H   CH.sub.3 CH.sub.3                                110                                                                              CF.sub.3                                                                          1 H   H    2-F    H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                          111                                                                             CF.sub.3                                                                          2 H   H    2-F    H   CH.sub.2CH.sub.2                                 112                                                                              CF.sub.3                                                                          2 H   H    2-F    H   CH.sub.2CH.sub.2                                 113                                                                              CF.sub.2                                                                          1 H   H    2-F    H   CH.sub.2CH.sub.2CH.sub.2                         114                                                                              CF.sub.3                                                                          1 H   H    3-CF.sub.3                                                                           H   CH(CH.sub.3)CH.sub.2                                                                            b.p. 70-71°                                                            0.08 mbar                      115                                                                              CF.sub.3                                                                          1 H   H    4-F    H   CH(CH.sub.3)CH.sub.2                                                                            b.p. 80-81°                                                            0.08 mbar                      116                                                                              CF.sub.3                                                                          1 H   H    3-CF.sub.3                                                                           H   CH.sub.2CH.sub.2  b.p. 70-72°                                                            0.04 mbar                      117                                                                              CF.sub.3                                                                          1 H   3-CH.sub.3                                                                         4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2  b.p. 92-94°                                                            0.02 mbar                      118                                                                              CF.sub.3                                                                          2 H   H    4-Cl   H   CH.sub.2CH.sub.2  b.p. 110-114°                                                          0.04 mbar                      119                                                                              CF.sub.3                                                                          1 H   H    4-F    H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        b.p. 80-82°                                                            0.4 mbar                       120                                                                              C.sub.2 H.sub.5                                                                   1 H   H    H      H   CH(CH.sub.3)CH.sub.2                                                                            b.p. 87-90°                                                            0.13 mbar                      121                                                                              C.sub.2 F.sub.5                                                                   1 H   H    H      H   CH(CH.sub.3)CH.sub.2                                                                            b.p. 78-90°                                                            0.15 mbar                      122                                                                              CF.sub.3                                                                          1 H   H    H      H   CH(CH.sub.3)CH.sub.2CH.sub.2                                                                    b.p. 91-93°                                                            0.08 mbar                      123                                                                              CF.sub.3                                                                          1 H   H    H      H   CH(CH.sub.3)CH.sub.2                                                                            b.p. 85-86°                                                            0.05 mbar                      124                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH(CH.sub.3)CH.sub.2CH.sub.2                                                                    b.p. 97-99°                                                            0.08 mbar                      125                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH(CH.sub.3)CH.sub.2                                                                            b.p. 94-96°                                                            0.05 mbar                      126                                                                              CF.sub.3                                                                          1 H   H    3-CF.sub.3                                                                           H   CH(CH.sub.3)CH.sub.2                                                                            b.p. 80-81°                                                            0.08 mbar                      127                                                                              CF.sub.3                                                                          1 H   H    4-F    H   CH(CH.sub.3)CH.sub.2                                                                            b.p. 82-84°                                                            0.12 mbar                      128                                                                              CF.sub.3                                                                          1 H   H    H      H   CH(C.sub.2 H.sub.5)CH.sub.2                                                                     b.p. 80-82                                                                    0.03 mbar                      129                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH(CH.sub.3)CH(CH.sub.3)                                                                        b.p. 97-99°                                                            0.15 mbar                      130                                                                              CF.sub.3                                                                          1 H   H    3-CF.sub.3                                                                           H   CH.sub.2CH.sub.2CH.sub.2                                                                        b.p. 88-90°                                                            0.15 mbar                      131                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2CH.sub.2CH.sub.2                                                                b.p. 93-94°                                                            0.09 mbar                      132                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2 CHCHCH.sub.2                                                                           b.p. 92-93°                                                            0.05 mbar                      133                                                                              CF.sub.3                                                                          1 H   H    2-Cl   H   CH.sub.2CH.sub.2  b.p. 91-92°                                                            0.09 mbar                      134                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2  b.p. 82-83°                                                            0.04 mbar                      135                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2 CHCHCH.sub.2                                                                           b.p. 107-109°                                                          0.08 mbar                      136                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2C(CH.sub.3).sub.2CH.sub.2                                                               b.p. 104-106°                                                          0.09 mbar                      137                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   CH.sub.2C(CH.sub.3).sub.2CH.sub.2                138                                                                              CF.sub.3                                                                          1 H   H    2-Cl   H   CH.sub.2C(CH.sub.3).sub.2CH.sub.2                139                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   CH(CH.sub.2)CH.sub.2                             140                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2CH.sub. 2                        141                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   CH.sub.3 CH.sub.3                                142                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         143                                                                              CF.sub.3                                                                          2 H   H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2                                 144                                                                              CF.sub.3                                                                          2 H   H    2-Cl   H   CH.sub.2CH.sub.2                                 145                                                                              CF.sub.3                                                                          2 H   H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2CH.sub.2                         146                                                                              CF.sub.3                                                                          2 H   H    4-Cl   H   CH.sub.2CH.sub.2CH.sub.2                         147                                                                              CF.sub.3                                                                          2 H   H    H      H   CH.sub.2CH.sub.2CH.sub.2                         148                                                                              CF.sub.3                                                                          2 H   H    2-Cl   H   CH.sub.2CH.sub.2CH.sub.2                         149                                                                              CF.sub.3                                                                          2 H   H    3-CH.sub.3                                                                           H   CH.sub.2CH.sub.2CH.sub.2                         150                                                                              CF.sub.3                                                                          2 H   H    3-CH.sub.3                                                                           H   CH.sub.2CH.sub.2CH.sub.2                         151                                                                              CF.sub.3                                                                          2 H   H    H      H   CH.sub.2CH.sub.2                                  ##STR44##                                                                    161                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2                                 162                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2                                  ##STR45##                                                                    171    1 H   H    H      H   CH.sub.2CH.sub.2                                 172    1 H   H    4-Cl   H   CH.sub.2CH.sub.2                                  ##STR46##                                                                    181                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.3 CH.sub.3                                182                                                                              CF.sub.3                                                                          1 H   H    H      H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                         183                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2                                 184                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2                                 185                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                          ##STR47##                                                                    186                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2                                 187                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2                                 188                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2                                 189                                                                              CF.sub.3                                                                          1 H   H    4-F    H   CH.sub.2CH.sub.2                                 190                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2CH.sub.2                         191                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2CH.sub.2                          ##STR48##                                                                    192                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2                                 193                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2                                 194                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2                                 195                                                                              CF.sub.3                                                                          1 H   H    4-F    H   CH.sub.2CH.sub.2                                 196                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2CH.sub.2                         197                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2CH.sub.2-                         ##STR49##                                                                    201                                                                              CF.sub.3                                                                          1 H   H    H      H   CH.sub.2CH.sub.2                                 202                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   CH.sub.2CH.sub.2                                 203                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   CH.sub.2CH.sub.2                                 204                                                                              CF.sub.3                                                                          1 H   H    4-F    H   CH.sub.2CH.sub.2                                  ##STR50##                                                                    211                                                                              CF.sub.3                                                                          1 H   H    H      H   2-furanyl                                        212                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   2-furanyl         b.p.                                                                          89-99° C./                                                             0.07 mbar                      213                                                                              CF.sub.3                                                                          1 H   H    4-F    H   2-furanyl                                        214                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   2-furanyl                                        215                                                                              CF.sub.3                                                                          1 H   H    2-Cl   H   2-furanyl                                        216                                                                              CF.sub.3                                                                          1 H   3-CH.sub.3                                                                         4-CH.sub.3                                                                           H   2-furanyl                                        217                                                                              CF.sub.3                                                                          1 H   H    3-CF.sub.3                                                                           H   2-furanyl                                        218                                                                              CF.sub.3                                                                          1 H   H    H      H   2-furanyl                                        219                                                                              CF.sub.3                                                                          1 H   H    H      H   2-pyranyl                                        220                                                                              CF.sub.3                                                                          1 H   H    4-Cl   H   2-pyranyl                                        221                                                                              CF.sub.3                                                                          1 H   H    4-CH.sub.3                                                                           H   2-pyranyl                                        __________________________________________________________________________

EXAMPLE 5 Formulation examples for compounds of formula I or mixturesthereof with herbicides (percentages are by weight)

    ______________________________________                                        (a) Wettable powders (a)     (b)     (c)                                      ______________________________________                                        Compound of formula I or mixtures                                                                  20%     60%       0.5%                                   thereof with a herbicide                                                      sodium lignosulfonate                                                                              5%      5%      5%                                       sodium laurylsulfate 3%      --      --                                       sodium diisobutylnaphthtalenesulfonate                                                             --      6%      6%                                       octylphenol polyethylene glycol ehter                                                              --      2%      2%                                       (7-8 moles of ethylene oxide)                                                 highly dispersed silicid acid                                                                      5%      27%     27%                                      kaolin               67%     --      --                                       sodium chloride      --      --       59.5%                                   ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        (b) Emulsifiable concentrate                                                                           (a)     (b)                                          ______________________________________                                        Compound of formula I or mixture thereof                                                               10%     1%                                           with a herbicide                                                              octylphenol polyethylene glycol ether                                                                   3%     3%                                           (4-5 moles of ethylene oxide)                                                 calcium dodecylbenzenesulfonate castor oil                                                              4%     4%                                           polyglycol ether (36 moles of ethylene oxide)                                 cyclohexanone            30%     10%                                          xylene mixture           50%     79%                                          ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        (c) Dusts               (a)     (b)                                           ______________________________________                                        Compound of formula I or mixture thereof                                                               0.1%    1%                                           with a herbicide                                                              talcum                  99.9%   --                                            kaolin                  --      99%                                           ______________________________________                                    

Dusts which are ready for use are obtained by mixing the activeingredient with the carriers, and grinding the mixture in a suitablemill.

    ______________________________________                                        (d) Extruder granulate  (a)     (b)                                           ______________________________________                                        Compound of formula I or mixture thereof                                                              10%     1%                                            with a herbicide                                                              sodium lignosulfonate   2%      2%                                            carboxymethylcellulose  1%      1%                                            kaolin                  87%     96%                                           ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        (e) Coated granulate                                                          ______________________________________                                        Compound of formula I or mixture thereof                                                               3%                                                   with a herbicide                                                              polyethylene glycol 200  2%                                                   kaolin                   94%                                                  ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        (f) Suspension concentrate                                                                            (a)      (b)                                          ______________________________________                                        Compound of formula I or mixture thereof                                                              40%      5%                                           with a herbicide                                                              ethylene glycol         10%      10%                                          nonylphenol polyethylene glycol ether                                                                  6%      1%                                           (15 moles of ethylene oxide)                                                  sodium lignosulfonate   10%      5%                                           carboxymethylcellulose   1%      1%                                           37% aqueous formaldehyde solution                                                                       0.2%     0.2%                                       silicone oil in the form of a 75%                                                                       0.8%     0.8%                                       aqueous emulsion                                                              water                   32%      77%                                          ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        Compound of formula I or mixture thereof                                                               5%                                                   with a herbicide                                                              isopropylamine           1%                                                   octylphenol polyethylene glycol ether                                                                  3%                                                   (78 moles of ethylene oxide)                                                  water                    91%                                                  ______________________________________                                    

BIOLOGICAL EXAMPLES

The ability of the compounds of formula I to protect cultivated plantsfrom the phytotoxic effects of potent herbicides is illustrated in thefollowing Examples. In the test procedures the compounds of formula Iare referred to as antidotes.

EXAMPLE 6 Test with antidote and herbicide in maize Preemergence ppiapplication of antidote and herbicide as tank mixture

The compound for testing as safener is sprayed onto the soil togetherwith the herbicide and the mixture is then incorporated into the soil.Plastic containers measuring 25 cm×17 cm×10 cm are then filled with thetreated soil and LG 5 maize seeds are sown therein. The protectiveaction of the safener is then evaluated (in %) 21 days afterapplication. The plants treated with herbicide alone and the completelyuntreated plants are used for reference purposes. A good (significant)safener effect is achieved if the phytoxicity of severe to average plantdamage can be reduced to slight, reversible damage or to completetolerance. A protective action of at least 25% is normally sufficientfor this. The results are reported below.

    ______________________________________                                        Herbicide: S--ethyl dipropylthiocarbamate "EPTC"                              Antidote: 1-(4-chlorophenyl)-1-(3,5-dioxolan-2-ylmethoximino)-                2,2,2-trifluoroethane (compound 40).                                                                      Protective action                                            Herbicide                                                                             antidote in %                                              ______________________________________                                        Rate of application in                                                                     8         --        0                                            kg/Hectare   8         8        38                                                         8         4        50                                                         8         2        75                                                         4         --        0                                                         4         4        50                                                         4         2        75                                                         4         1        75                                            ______________________________________                                    

EXAMPLE 7 Preemergence test with antidote and herbicide in sorghumApplication of the antidote by seed dressing

Funk G 522 sorghum seeds are mixed with the compound for testing assafener in a glass beaker. Seeds and compound are thoroughly mixed byshaking and rotating the beaker. Then plastic containers measuring 25cm×17 cm×12 cm are filled with sandy loam and the dressed seeds are sowntherein. The seeds are covered and the herbicide is then sprayed ontothe surface of the soil. The protective action of the safener isevaluated (in %) 19 days after application. The plants treated withherbicide alone and the completely untreated controls are used forreference purposes. The results are reported below.

    ______________________________________                                        Herbicide: N--chloroacetyl-N--(2-methoxy-1-methylethyl)-2-                    ethyl-6-methyl-aniline ("metolachlor").                                       Antidote: 1-(4-chlorophenyl)-1-(3,5-dioxolan-2-ylmethoximino)-                2,2,2-trifluoroethane (compound 40).                                          Rate of application in kg/hectare                                                                  Protective action                                        Herbicide    antidote    in %                                                 ______________________________________                                        4            0            0                                                   4            1           38                                                   4            0.5         63                                                   4            0.25        63                                                   2            0            0                                                   2            1           38                                                   2            0.5         63                                                   2            0.25        63                                                   2            0.125       63                                                   1            0            0                                                   1            1           50                                                   1            0.5         63                                                   1            0.25        75                                                   1            0.125       88                                                   ______________________________________                                    

Other tests result in the following values:

    ______________________________________                                        Rate of application in kg/hectare                                                                  Protective action                                        Herbicide    antidote    in %                                                 ______________________________________                                        4            0            0                                                   4            2           50                                                   4            1           63                                                   4            0.5         63                                                   Rate of application in kg/ha                                                                      Protective action                                         Herbicide    antidote   in %                                                  ______________________________________                                        2            0          `10                                                   2            2          50                                                    2            1          63                                                    2            0.5        63                                                    1            0           0                                                    1            2          50                                                    1            1          63                                                    1            0.5        63                                                    Rate of application in kg/hectare                                                                  Protective action                                        Herbicide    antidote    in %                                                 ______________________________________                                        2            0            0                                                   4            4           50                                                   4            2           63                                                   4            1           63                                                   2            0            0                                                   2            4           50                                                   2            2           50                                                   2            1           50                                                   2            0.5         50                                                   1            0            0                                                   1            4           25                                                   1            2           25                                                   1            1           38                                                   1            0.5         50                                                   ______________________________________                                    

In a further test, N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline("alachlor") is used as herbicide and1-(4-chlorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane(compound 40) as antidote.

    ______________________________________                                        Rate of application in kg/hectare                                                                  Protective action                                        Herbicide    antidote    in %                                                 ______________________________________                                        4            0            0                                                   4            2           63                                                   4            1           75                                                   2            0            0                                                   2            4           50                                                   2            2           63                                                   2            1           75                                                   2            0.5         75                                                   1            0            0                                                   1            4           38                                                   1            2           50                                                   1            1           63                                                   1            0.5         63                                                   ______________________________________                                    

EXAMPLE 8 Test with antidote and herbicide in sorghum Preemergenceapplication of herbicide and antidote as tank mixture

Plastic containers measuring 25 cm×17 cm×12 cm are filled with sandyloam and Funk G 522 sorghum seeds are sown therein. The seeds arecovered and the compound for testing as safener is then sprayed,together with the herbicide, in dilute solution as tank mixture onto thesurface of the soil. The protective action of the safener is evaluated(in %) 30 days after application. The plants treated with herbicidealone and the completely untreated controls are used for referencepurposes. The results are reported below.

    ______________________________________                                        Herbicide: N--chloroacetyl-N--(2-methoxy-1-methyl)-2-ethyl-                   6-methyl-aniline ("metolachlor").                                             Antidote: 1-(4-chlorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-                2,2,2-trifluoroethane (compound 40).                                          Rate of application in kg/hectare                                             ______________________________________                                        Herbicide +                                                                              4      4    4    2   2    2    1    1  1                           antidote   0      4    2    0   2    1    0    1    0.5                       Protective action                                                                        0     63    63   0   63   63   0   50  50                          in %                                                                          ______________________________________                                    

In a further test, N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline isused as herbicide and1-(4-chlorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethaneas antidote. The test is carried out with Funk G 522 sorghum seedwithout the addition of weeds.

    ______________________________________                                        Rate of application in kg/hectare                                                                  Protective action                                        Herbicide    antidote    in %                                                 ______________________________________                                        2            0            0                                                   2            2           75                                                   2            1           88                                                   1            0            0                                                   1            1           75                                                   1            0.5         75                                                   ______________________________________                                    

EXAMPLE 9 Test with antidote and herbicide in soybeans Preemergenceapplication of herbicide and antidote as tank mixture

Pots (diameter at the top 6 cm) are filled with sandy loam and "Hark"soybean seeds are sown therein. The seeds are covered and the compoundfor testing as safener, together with the herbicide, is sprayed indilute solution as tank mixture onto the surface of the soil. Theprotective action is evaluated (in %) 21 days after application. Theplants treated with herbicide alone and the completely untreatedcontrols are used for reference purposes. The results are reportedbelow.

    ______________________________________                                        Herbicide: 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-tri-           azin-5-one ("metribuzin").                                                           Rate of application                                                                         Relative protective                                             antidote                                                                              Herbicide action                                               ______________________________________                                        No. 1    1.5 kg/ha 0.75 kg/ha                                                                              25%                                              No. 2    1.5 kg/ha 0.75 kg/ha                                                                              25%                                               No. 11  1.5 kg/ha 0.75 kg/ha                                                                              25%                                              ______________________________________                                    

EXAMPLE 10 Test with antidote and herbicide in wheat Postemergenceapplication of herbicide and antidote as tank mixture

"Farnese" wheat seeds are sown in plastic pots (diameter at the top 11cm) containing 0.5 liter of earth in a greenhouse. The seeds are coveredand the compound for testing as safener is applied postemergence,together with the herbicide, as tank mixture. The protective action ofthe safener is evaluated (in %) 20 days after application. The plantstreated with herbicide alone and the completely untreated controls areused for reference purposes. The results are reported below:

    ______________________________________                                        Herbicide: Propargyl α-[4-(2,4-dichloropyridyl-2-oxy)phenoxy]-          propionate.                                                                   Rate of application                                                           antidote    Herbicide Relative protective action                              ______________________________________                                        No. 2  1.5 kg/ha                                                                              0.75 kg/ha                                                                              25%                                                 No. 40 1.5 kg/ha                                                                              0.75 kg/ha                                                                              25%                                                 No. 41 1.5 kg/ha                                                                              0.75 kg/ha                                                                              25%                                                 No. 65 1.5 kg/ha                                                                              0.75 kg/ha                                                                              50%                                                 ______________________________________                                    

EXAMPLE 11 Test with antidote and herbicide in rice Application of theantidote during immersion of the rice seeds, and preemergenceapplication of the herbicide to the moist soil

Rice seeds are immersed for 48 hours in 100 ppm solutions of thecompound for testing as safener. The seeds are then allowed to dry forabout 2 hours until they are no longer tacky. Plastic containersmeasuring 25 cm×17 cm×12 cm are filled with sandy loam to 2 cm below theedge. The pretreated seeds are sown on the surface of the soil in thecontainers and only lightly covered. The soil is kept in a moist(non-marshy) state. Then a dilute solution of the herbicide is sprayedonto the surface of the soil. The water level is then gradually raisedin accordance with growth of the rice plants. The protective action ofthe safener is evaluated (in %) 18 days after application. The plantstreated with herbicide alone and the completely untreated controls areused for reference purposes. The results are as follows:

    ______________________________________                                        Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethyl)acetamide               ("pretilachlor").                                                             Rate of application                                                           antidote    Herbicide Relative protective action                              ______________________________________                                        No. 63 100 ppm  0.25 kg/ha                                                                              25%                                                 ______________________________________                                    

EXAMPLE 12 Test with antidote and herbicide in rice Application of theantidote as seed dressing and premergence application of the herbicideto the moist soil

Rice seeds are mixed with the compound for testing as safener in a glassbeaker. Seeds and compound are thoroughly mixed by shaking and rotating.Containers measuring 47 cm×29 cm×24 cm are then filled with sandy loamand the dressed seeds are sown therein. The seeds are covered and theherbicide is then sprayed in dilute solution onto the surface of thesoil. About 20 days after sowing when the rice plants are in the 3-leafstage, the surface of the soil is covered with water to a height of 4cm. The protective action of the safener is evaluated (in %) 30 daysafter the application of the herbicide. The plants treated withherbicide alone and the completely untreated controls are used forreference purposes. The results are as follows:

    ______________________________________                                        Rate of application  Relative protective                                      antidote      Herbicide  action                                               ______________________________________                                        Herbicide: 2,6-dinitro-N,N--dipropyl-4-trifluoromethylaniline                 ("tri-fluralin").                                                             No. 40                                                                              2 g/kg of seeds                                                                           2      kg/ha 25%                                            No. 40                                                                              2 g/kg of seeds                                                                           1      kg/ha 38%                                            ______________________________________                                        Herbicide: Methyl-α-[4-(2,4-dichlorophenoxy)phenoxy]propionate          ("hoelon").                                                                   No. 40                                                                              1 g/kg of seeds                                                                           1      kg/ha 50%                                            No. 40                                                                              2 g/kg of seeds                                                                           0.5    kg/ha 63%                                            No. 40                                                                              1 g/kg of seeds                                                                           1      kg/ha 25%                                            No. 40                                                                              1 g/kg of seeds                                                                           0.5    kg/ha 38%                                            ______________________________________                                        Herbicide: Propargyl α-[4-(2',4'-dichloropyridyl-2'oxy)phenoxy]-        propionate.                                                                   No. 40                                                                              2 g/kg of seeds                                                                           0.5    kg/ha 50%                                            No. 40                                                                              2 g/kg of seeds                                                                           0.25   kg/ha                                                ______________________________________                                    

What is claimed is:
 1. An oxime ether of the formula ##STR51## wherein nis 1 or 2 each of R₁ and R₂ is hydrogen or C₁ -C₄ -alkyl,each of R₃ andR₄ is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy,C₁ -C₄ haloalkoxy or nitro R₅ and R₆ are independently of each other C₁-C₄ alkyl or C₃ -C₄ alkenyl X is a fluorinated C₁ -C₃ alkyl radicalwhich may also additionally contain chlorine and Y is hydrogen, C₁ -C₄alkyl or C₁ -C₄ alkoxy.
 2. An oxime ether of claim 1 wherein n is 1, R₁and R₂ are hydrogen, R₃ and R₄ are hydrogen or halogen, R₅ and R₆ are C₁-C₄ alkyl, X is trifluoromethyl and Y is hydrogen. 3.1-Phenyl-1-(2,2-dimethoxy-ethoximino)-2,2,2-trifluoroethane of claim 1.4. 1-Phenyl-1-(2,2-diethoxy-ethoximino)-2,2,2-trifluoroethane ofclaim
 1. 5.1-(4-Chlorophenyl)-1-(2,2-dimethoxy-ethoximino)-2,2,2-trifluoroethane ofclaim
 1. 6.1-(4-Chlorophenyl)-1-(2,2-diethoxy-ethoximino)-2,2,2-trifluoroethane ofclaim
 1. 7.1-(4-Fluorophenyl)-1-(2,2-dimethoxy-ethoximino)-2,2,2-trifluoroethane ofclaim
 1. 8.1-(4-Fluorophenyl)-1-(2,2-diethoxy-ethoximino)-2,2,2-trifluoroethane ofclaim
 1. 9. A composition for controlling weeds in crops of cultureplants which comprises (a) a herbicidally effective amount of aherbicide selected from the group consisting of thiocarbamates,haloacetanilides, phenoxyphenoxypropionates,pyridyloxyphenoxypropionates and dinitroanilines, and (b) as cropsafening agent an oxime ether of the formula ##STR52## wherein n is 1 or2 each of R₁ and R₂ is hydrogen or C₁ -C₄ -alkyl,each of R₃ and R₄ ishydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkyoxy or nitro, R₅ and R₆ are independently of each other C₁ -C₄alkyl or C₃ -C₄ alkenyl X is a fluorinated C₁ -C₃ alkyl radical whichmay also additionally contain chlorine and Y is hydrogen, C₁ -C₄ alkylor C₁ -C₄ alkoxy.
 10. A composition of claim 9 in which the herbicide isa haloacetanilide of the formula ##STR53## wherein each of R₈ and R₉ ishydrogen, halogen, lower alkyl or lower alkoxy, Z is hydrogen or loweralkyl, A is methylene, 1-1-ethylene or 1,2-ethylene, each of which isoptionally substituted by 1 or 2 lower alkyl groups, and R₁₀ is loweralkoxy, allyloxy, lower alkoxycarbonyl, N,N-di(lower alkyl)-carbamoyl,N-propargylcarbamoyl, cyano, ethynyl, 1,3-dioxolan-2-yl,2-tetrahydrofuranyl, optionally substituted benzoyl, optionallysubstituted 1,3,4-oxadiazol-2-yl or optionally substituted1,3,4-triazol-2-yl.
 11. A method of protecting rice, sorghum, wheat andmaize crops from the phytoxic action of thiocarbamate, triazinonehaloacetanilide, phenoxyphenoxypropionate pyridyloxyphenoxypropionate ordinitroaniline herbicides, which comprises adding to the herbicides,applying to the locus of the crops, or applying to the seeds of saidcrops, as antidote, a compound of the formula ##STR54## wherein n is 1or 2 each of R₁ and R₂ is hydrogen or C₁ -C₄ -alkyl,each of R₃ and R₄ ishydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy or nitro, R₅ and R₆ are independently of each other C₁ -C₄alkyl or C₃ -C₄ alkenyl X is a fluorinated C₁ -C₃ alkyl radical whichmay also additionally contain chlorine and Y is hydrogen, C₁ -C₄ alkylor C₁ -C₄ alkoxy.
 12. A method of claim 11 in which the compound is1-phenyl-1-(2,2-dimethoxy-ethoximino)-2,2,2-trifluoroethane.
 13. Amethod of claim 11 in which the compound is1-(4-chlorophenyl)-1-(2,2-dimethoxyethoximino)-2,2,2-trifluoroethane.14. A method of claim 11 in which the compound is1-(4-chlorophenyl)-1-(2,2-diethoxy-ethoximino)-2,2,2-trifluoroethane.15. A method of claim 11 in which the herbicide is 4-amino-6-tertbutyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one.
 16. A method ofclaim 11 in which the herbicide ispropargyl-[4-(2,4-dichloropyridyl-2-oxy)-phenoxy]-propionate.